M. Pellarin

Quantitative Determination of the Size Dependence of Surface Plasmon Resonance Damping in Single Ag@SiO2 Nanoparticles

The optical extinction spectra of single silver nanoparticles coated with a silica shell were investigated in the size range 10-50 nm. Measurements were performed using the spatial modulation spectroscopy technique which permits independent determination of both the size of the metal nanoparticle under study and the width of its localized surface plasmon resonance (LSPR). These parameters can thus be directly correlated at a single particle level for the first time. The results show a linear increase of the width of the LSPR with the inverse diameter in the small size regime (less than 25 nm). For these nanoparticles of well-controlled environment, this can be ascribed to quantum confinement of electrons or, classically, to increase of the electron surface scattering processes. The impact of this effect was measured quantitatively and compared to the predictions by theoretical models.

FROM FREE CLUSTERS TO CLUSTER-ASSEMBLED MATERIALS

In this paper the specific properties of free clusters and the formation of new cluster-assembled materials using the low energy cluster beam deposition (LECBD) technique are discussed. Recent results obtained for free clusters are summarized with special attention to new observed structures. As for the specific structures and properties of cluster-assembled materials, two main aspects are specially emphasized: the memory effect of the free cluster properties leading to the formation of new phases and the effect of the specific nanostructure of the cluster-assembled materials related to the random cluster stacking mechanism characteristic of the LECBD. These effects and the corresponding potential applications are illustrated using some selected examples: new diamond-like carbon films produced by fullerene depositions (memory effect) and grain effect on the magnetic properties of cluster-assembled transition metal films.

Evidence for icosahedral atomic shell structure in nickel and cobalt clusters. Comparison with iron clusters

Abstract For the first time, the mass distribution of nickel, cobalt and iron clusters is analyzed in a large mass range with near threshold photoionization experiments and standard time-of-flight mass spectrometry. In the case of nickel and cobalt, oscillations observed in mass spectra correspond to icosahedral atomic shell structure in the studied mass range (50–800 atoms). For iron clusters, the situation is less clear. The exact location of structures in mass spectra depends on source operating conditions. We have observed the competition between different cluster geometries.

Photolysis experiments on SiC mixed clusters: From silicon carbide clusters to silicon-doped fullerenes

Silicon carbon binary clusters are generated in a laser vaporization source from SixC1−x mixed targets (x=0 to 50%). We have first analyzed stoichiometric (SiC)n (n⩽40) clusters grown from a silicon carbide target (x=50%). Both high fluence photoionization of (SiC)n neutral clusters and photofragmentation of size-selected (SiC)n+ natural positive ions show that silicon-doped fullerenes emerge as stable photoproducts through the laser induced annealing of these clusters. They are detected as stable species as soon as a sufficient amount of silicon is eliminated through unimolecular processes involving the sequential losses of Si2C and Si3C neutral molecules in the earliest evaporation steps. This result is in favor of an efficient substitution of silicon atoms (about 12) into stable “cagelike” carbon networks. We will also show that an efficient doping of carbon fullerenes with silicon atoms can be obtained in carbon-rich mixed clusters directly grown as positive ions from nonstoichiometric targets (x<25%). Mass abundance spectroscopy gives a clear signature of cagelike structures where silicon atoms are substituted for carbon ones. The results on the favored stability of even-numbered C2n−qSiq+ clusters with q=0, 1, 2 are presented here in the size range: 2n=32–80. More largely doped species (q⩾3) cannot be evidenced in abundance mass spectroscopy because of unavoidable mass coincidences. A careful analysis of the photofragmentation behavior of selected sizes relative to the laser fluence nevertheless succeeds in indicating the contribution to the photofragmentation spectra of largely doped heterofullerenes C2n−qSiq+ (q=7 at least) that mainly dissociate by the loss of small even-numbered mixed molecules such as Si2,Si3C,… . Both approaches are consistent with the surprising capability of substituting a large number of silicon atoms into fullerenes without destabilizing their cage structure too much. In this respect, a value close to 12 seems to be an upper limit.Silicon carbon binary clusters are generated in a laser vaporization source from SixC1−x mixed targets (x=0 to 50%). We have first analyzed stoichiometric (SiC)n (n⩽40) clusters grown from a silicon carbide target (x=50%). Both high fluence photoionization of (SiC)n neutral clusters and photofragmentation of size-selected (SiC)n+ natural positive ions show that silicon-doped fullerenes emerge as stable photoproducts through the laser induced annealing of these clusters. They are detected as stable species as soon as a sufficient amount of silicon is eliminated through unimolecular processes involving the sequential losses of Si2C and Si3C neutral molecules in the earliest evaporation steps. This result is in favor of an efficient substitution of silicon atoms (about 12) into stable “cagelike” carbon networks. We will also show that an efficient doping of carbon fullerenes with silicon atoms can be obtained in carbon-rich mixed clusters directly grown as positive ions from nonstoichiometric targets (x<25%)...

Resonant Raman scattering by quadrupolar vibrations of Ni-Ag core-shell nanoparticles

Low-frequency Raman-scattering experiments have been performed on thin films consisting of nickel-silver composite nanoparticles embedded in alumina matrix. It is observed that the Raman scattering by the quadrupolar modes, strongly enhanced when the light excitation is resonant with the surface dipolar excitation, is mainly governed by the silver electron contribution to the plasmon excitation. The Raman results are in agreement with a core-shell structure of the nanoparticles, the silver shell being loosely bonded to the nickel core.

Functional nanostructures from clusters

Functional cluster-assembled nanostructures with original structures and properties are prepared using the Low Energy Cluster Beam Deposition method (LECBD). This technique consists in depositing supersonic clusters produced in the gas phase using a combined laser vapourisation-inert gas condensation source. Low energy clusters with typical sizes ranging from ∼1 to a few nm are not fragmented upon impact on the substrate (soft landing regime) leading to the formation of cluster-assembled nanostructures which retain the original structures and properties of the incident free clusters. Model nanostructured systems of any kind of materials (metallic, covalent, oxides) well suited for fundamental studies in various fields (nanoelectronics, nanomagnetism, nanophotonics, catalysis or nanobiology) and for applications to very high integration-density devices (∼Tbits/in/²) are prepared using this method. After a brief review of techniques to produce, analyse, mass select, and deposit clusters in the LECBD-regime, the specific aspects of the nucleation and growth process which govern the formation of cluster-assembled nanostructures on the substrate are presented, especially the preparation of 2D-organised arrays of cluster-assembled dots by depositing low energy clusters on FIB-functionalised substrates. Characteristic examples of cluster systems prepared by LECBD are also described: i) metallic (Au, Ag, Au-Ag, Ag-Ni, Ag-Pt)) and oxide (Gd2O3, ZnO) cluster-assembled nanostructures for applications to linear and non linear nano-optics; ii) magnetic nanostructures from Co-based nanoclusters (i.e., Co-Pt) exhibiting a high magnetic anisotropy which is well suited for applications to high density data storage devices; iii) gold or Pd-Pt or Au-Ti clusters for chemical reactivity and catalysis applications. In some specific cases, we were able to perform studies from an isolated individual nanocluster up to 2D or 3D-collections of non-interacting or interacting particles leading to a rather good understanding of the intrinsic as well as the collective properties at nanoscale.

Nanostructured silicon films obtained by neutral cluster depositions

Nanosize neutral silicon clusters produced using a laser vaporization source were analyzed in the gas phase and deposited on various substrates at room temperature in ultrahigh vacuum. Nanostructured thin films with thickness around 100 nm resulting from this nearly ballistic deposition process were subsequently characterized by several complementary electron spectroscopy techniques to investigate the electronic structure. The film properties are comparable to those of a disordered phase but different from the properties of conventional amorphous or nanoporous silicon. The specific features observed in the Si-cluster assembled films cannot be simply interpreted on the basis of quantum confinement effects and are rather attributed to the presence of odd-membered rings in the incident-free cluster structure. Some Si-cluster geometries in the subnanometric size range are proposed and discussed on the basis of the experimental results and a tight binding scheme.

Shell structure in photoionization spectra of large aluminum clusters

Photoionization mass spectrometry experiments, performed on an extensive size range of aluminum clusters produced by laser vaporization technique, are reported. Ionization potential values are deduced from individual photoionization efficiency curves for the smaller AlN clusters (N=36–112). Our results confirm and complete those previously published. The mass spectra of larger clusters (N≊250–1400) reveal a regular signal oscillation. Several additional experiments give proof that this striking pattern originates from size‐dependent ionization threshold effects. This structure exhibits exact periodicity as a function of N1/3 or Ne1/3 (Ne the number of valence electrons).

Synthesis, electron tomography and single-particle optical response of twisted gold nano-bipyramids.

A great number of works focus their interest on the study of gold nanoparticle plasmonic properties. Among those, sharp nanostructures appear to exhibit the more interesting features for further developments. In this paper, a complete study on bipyramidal-like gold nanostructures is presented. The nano-objects are prepared in high yield using an original method. This chemical process enables a precise control of the shape and the size of the particles. The specific photophysical properties of gold bipyramids in suspension are ripened by recording the plasmonic response of single and isolated objects. Resulting extinction spectra are precisely correlated to their geometrical structure by mean of electron tomography at the single-particle level. The interplay between the geometrical structure and the optical properties of twisted gold bipyramids is further discussed on the basis of numerical calculations. The influence of several parameters is explored such as the structural aspect ratio or the tip truncation. In the case of an incident excitation polarized along the particle long axis, this study shows how the plasmon resonance position can be sensitive to these parameters and how it can then be efficiently tuned on a large wavelength range.

Absolute optical extinction measurements of single nano-objects by spatial modulation spectroscopy using a white lamp

This article describes a high sensitivity spectrophotometer designed to detect the overall extinction of light by a single nanoparticle (NP) in the 10(-4)-10(-5) relative range, using a transmission measurement configuration. We focus here on the simple and low cost scheme where a white lamp is used as a light source, permitting easy and broadband extinction measurements (300-900 nm). Using a microscope, in a confocal geometry, an increased sensitivity is reached thanks to a modulation of the NP position under the light spot combined with lock-in detection. Moreover, it is shown that this technique gives access to the absolute extinction cross-sections of the single NP provided that the incident electromagnetic field distribution experienced by the NP is accurately characterized. In this respect, an experimental procedure to characterize the light spot profile in the focal plane, using a reference NP as a probe, is also laid out. The validity of this approach is discussed and confirmed by comparing experimental intensity distributions to theoretical calculations taking into account the vector character of the tightly focused beam. The calibration procedure permitting to obtain the absolute extinction cross-section of the probed NP is then fully described. Finally, the force of the present technique is illustrated through selected examples concerning spherical and slightly elongated gold and silver NPs. Absolute extinction measurements are found to be in good consistency with the NP size and shape independently obtained from transmission electron microscopy, showing that spatial modulation spectroscopy is a powerful tool to get an optical fingerprint of the NP.